The Q-Band Energetics and Relaxation of Chlorophylls a and b as Revealed by Visible-to-Near Infrared Time-Resolved Absorption Spectroscopy.

Chlorophyll (Chl) is the most abundant light-harvesting pigment of oxygenic photosynthetic organisms; however, the Q-band energetics and relaxation dynamics remain unclear. In this work, we have applied femtosecond time-resolved (fs-TA) absorption spectroscopy in 430-1,700 nm to Chls a and b in diluted pyridine solutions under selective optical excitation within their Q-bands. The results revealed distinct near-infrared absorption features of the Bx,y ← Qy and Bx,y ← Qx transitions in 930-1,700 nm, which together with the steady-state absorption in 400-700 nm unveiled the Qx(0,0)-state energy that lies 1,000 ± 400 and 600 ± 400 cm-1 above the Qy(0,0)-state for Chls a and b, respectively. In addition, the Qx-to-Qy internal conversion time constants are estimated to be less than 80 fs for Chls a and b. These findings may shed light on understanding the roles of the Chls in the primary excitation energy transfer reactions of photosynthesis.